CN114855195A - Self-balancing self-control high-purity dry hydrogen preparation system - Google Patents
Self-balancing self-control high-purity dry hydrogen preparation system Download PDFInfo
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- CN114855195A CN114855195A CN202110068688.7A CN202110068688A CN114855195A CN 114855195 A CN114855195 A CN 114855195A CN 202110068688 A CN202110068688 A CN 202110068688A CN 114855195 A CN114855195 A CN 114855195A
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
A self-balancing self-control high-purity dry hydrogen preparation system comprises: the galvanic pile is used for preparing hydrogen by electrolyzing water vapor by using electric energy; a material supply module for supplying a mixed gas containing water vapor and air to the electric pile; a scavenging module which returns part of the hydrogen discharged by the electric pile to the electric pile; the heat management module is used for carrying out heat management on the material supply module, the scavenging module and the galvanic pile; when leakage is detected, the safety guarantee module stops the operation of the galvanic pile and supplies safety gas to the galvanic pile; an external power supply for supplying power; and a control module; the control module controls the material supply module, the scavenging module and the thermal management module to recycle a plurality of gases discharged by the electric pile and heat carried by the gases in a mode of maintaining the electric pile to work in a specified working temperature range.
Description
Technical Field
The invention belongs to the technical field of hydrogen production, and particularly relates to a self-balancing self-control high-purity dry hydrogen preparation system.
Background
Hydrogen is an important secondary energy source, and is drawing attention due to its characteristics of various sources, environmental protection, storability, and the like. With the diversified adjustment of energy structures in China and the breakthrough of fuel cell and hydrogen station technologies, the demand of the market for hydrogen will increase greatly. At present, more than 90% of hydrogen in China comes from hydrocarbon and coal chemical industry, and a large amount of carbon dioxide is discharged in the production process.
The high-temperature electrolysis of water vapor to prepare green hydrogen by utilizing excess electric power such as wind energy or solar energy is a low-pollution and high-efficiency technology. The core of the high-temperature water vapor electrolysis hydrogen production technology is a high-temperature water electrolysis hydrogen production tank, which is an electrochemical device for producing hydrogen by electrolyzing water vapor at high temperature and generally consists of an air electrode, an electrolyte and a hydrogen electrode. They are classified into proton conductivity type and oxygen ion conductivity type according to the conductivity type of their electrolyte. The high-temperature proton conductor material is reported by Iwahara and the like to be used for hydrogen production by electrolyzing water, but the proton conductor type high-temperature electrolytic cell is not put into practical use for a long time due to the stability of the material and the like, and the technical development of the proton conductor type high-temperature electrolytic cell is changed day by day along with the development of novel materials and the improvement of the stability of the materials in recent years, wherein the Ba-based perovskite oxide material has better comprehensive performance and is widely researched.
However, there is no hydrogen production system based on proton conductor type stack, and the existing hydrogen production system cannot realize high energy efficiency of the system.
Disclosure of Invention
The problems to be solved by the invention are as follows:
in view of the above problems, the present invention aims to provide a self-balancing self-control high-purity dry hydrogen preparation system capable of preparing high-purity dry hydrogen, and having low energy consumption and high energy utilization rate.
The technical means for solving the problems are as follows:
in order to solve the above problems, the present invention provides a self-balancing and self-controlling high-purity dry hydrogen preparation system, comprising: the galvanic pile is used for preparing hydrogen by electrolyzing water vapor by using electric energy; a material supply module supplying a mixed gas containing water vapor and air to the electric pile; a scavenging module which returns part of the hydrogen discharged by the electric pile to the electric pile; a thermal management module for thermally managing the material supply module, the scavenging module and the galvanic pile; a safety and security module stopping the operation of the stack and supplying safety gas to the stack when leakage is detected; an external power supply for supplying power; and a control module; the control module controls the material supply module, the scavenging module and the thermal management module to circularly utilize a plurality of gases exhausted by the electric pile and heat carried by the gases in a mode of maintaining the electric pile to work in a specified working temperature interval.
In the present invention, the stack may include a plurality of electrolytic cells, a distributor that distributes hydrogen gas to the plurality of electrolytic cells, and a collector that collects hydrogen gas from the plurality of electrolytic cells; the plurality of electrolytic cells are proton conductor type electrolytic cells formed in a tubular shape, including an air electrode on the outside, a hydrogen electrode on the inside, and an electrolyte composed of a proton conductor material between the air electrode and the hydrogen electrode; the stack also includes a pair of high temperature resistant wires for introducing electrical current. According to this structure, it is possible to efficiently and stably produce high-purity dry hydrogen gas by a stack composed of a plurality of proton conductor-type electrolytic cells, and the produced hydrogen gas does not need further treatment.
In the present invention, the scavenging module may include: a hydrogen gas discharge line that discharges hydrogen gas from the stack; a hydrogen circulation line for supplying hydrogen to the stack; and a hydrogen heat exchanger for heat-exchanging the hydrogen in the hydrogen circulation line and the hydrogen in the hydrogen discharge line; a hydrogen outlet pressure sensor is arranged on the hydrogen discharge pipeline at the downstream side of the hydrogen heat exchanger; the hydrogen circulation pipeline is connected with the hydrogen discharge pipeline through a hydrogen circulation pump, and part of hydrogen in the hydrogen circulation pipeline is shunted to the hydrogen discharge pipeline. Thus, the high-temperature hydrogen generated by the stack can be recycled, and the low-temperature hydrogen supplied to the stack can be heated by the high-temperature hydrogen discharged by the stack, thereby realizing heat reuse.
In the present invention, the hydrogen circulation pipeline is provided with a hydrogen solenoid valve, a hydrogen inlet pressure sensor and a hydrogen mass flow controller at the upstream side of the hydrogen heat exchanger; the control module controls the hydrogen circulating pump and the hydrogen solenoid valve based on detection values of the hydrogen inlet pressure sensor and the hydrogen mass flow controller, and adjusts a hydrogen flow rate branched from the hydrogen circulating pipeline to the hydrogen exhaust pipeline.
In the present invention, the security module may include: a hydrogen sensing alarm; a safety gas pipeline provided with a safety gas electromagnetic valve, a safety gas pressure sensor and a safety gas mass flow controller; and connecting the safety gas pipeline with the hydrogen circulating pipeline through a three-way regulating valve; the safety guarantee module judges whether hydrogen leakage occurs according to detection values of the hydrogen inlet pressure sensor and the hydrogen outlet pressure sensor, and cuts off the external power supply when the leakage is judged to occur, controls the three-way regulating valve to block the hydrogen circulation pipeline and open the safety gas pipeline; the safety gas is nitrogen or inert gas. Therefore, hydrogen leakage which possibly occurs to parts and the galvanic pile can be detected and responded in time, and man-machine safety is ensured to prevent accidents.
In the present invention, the material supply module may include: an air heat exchanger; an air supply pipeline for supplying air to the air heat exchanger; a water pump is arranged, and a water supply pipeline is used for supplying water to the air heat exchanger; a steam supply line supplying steam to the air heat exchanger; a mixed gas line for sending the mixed gas from the air heat exchanger to the electric pile; a high-temperature wet tail gas pipeline connected with the air heat exchanger and used for discharging wet tail gas from the electric pile; and a low temperature wet tail gas line for discharging the low temperature wet tail gas after heat exchange from the air heat exchanger; a wet tail gas circulating pump is arranged on the lower side of the low-temperature wet tail gas pipeline, which is closer to the air heat exchanger than the low-temperature wet tail gas pipeline, and the wet tail gas circulating pump is branched out of the wet tail gas circulating pipeline; and the air, the water and the water vapor are subjected to heat exchange with wet tail gas in the wet tail gas circulating pipeline in the air heat exchanger and then heated and mixed to form the mixed gas.
In the invention, an oxygen concentration sensor and a moisture content sensor for analyzing gas components are arranged on the wet tail gas circulating pipeline; a wet tail gas outlet pressure sensor is arranged on the wet tail gas pipeline between the wet tail gas circulating pump and the air exchanger; an air inlet pressure sensor is also arranged on the air supply pipeline; the control module controls as follows: controlling the power of the wet tail gas circulating pump according to the detection value of the moisture content sensor, and returning a part of wet tail gas to the air heat exchanger; and controlling the power of the blower according to the comparison between the detection value of the oxygen concentration sensor in the wet tail gas circulating pipeline and the oxygen content value in the air, reducing the power of the blower when the detection value of the oxygen concentration sensor is high, and increasing the power of the blower when the detection value of the oxygen concentration sensor is low.
In the invention, a condensed water storage area for storing condensed water generated by heat exchange is formed at the lower part of the air heat exchanger, and the condensed water storage area is connected with the water pump through a condensed water pipeline; a liquid level sensor for monitoring the liquid level of the condensed water is arranged on the condensed water storage area; and the control module returns at least one part of the condensed water to the water pump for recycling according to the detection value of the liquid level sensor.
In the invention, the control module adjusts the water flow supplied by the water pump according to the difference between the moisture content required by the galvanic pile and the moisture content in the wet tail gas circulation pipeline and the moisture content in the water vapor supply pipeline; the water is deionized water.
In the present invention, a steam flow controller for detecting and controlling the flow of steam is further disposed on the steam supply pipeline; the control module adjusts the moisture content in the water vapor supply pipeline by controlling the water vapor flow controller according to the moisture content required by the galvanic pile, the moisture content in the wet tail gas circulation pipeline and the moisture content obtained by evaporating water supplied by the water pump in the air heat exchanger.
According to the structure, the water vapor on the air side of the electric pile can be recycled, the amount of the water vapor and the water vapor on the input side is reduced according to the recycling amount, self-balancing self control of the water vapor and the water vapor is achieved, high recycling of materials is achieved, and energy consumption of a system is reduced.
In the present invention, the thermal management system may include: a thermal balance heater disposed on the mixed gas pipeline; the heat balance insulation box is used for insulating the hydrogen heat exchanger, the air heat exchanger and the heat balance heater; a galvanic pile heat insulation box for insulating the galvanic pile; and a temperature sensor; the control module controls the heat balance heater to heat the mixed gas in a mode of ensuring that the electric pile works in a specified temperature interval according to the power output by the external power supply to the electric pile. Therefore, the heat management can be carried out on the hydrogen preparation system, and the energy consumption of the hydrogen preparation system is saved.
In the invention, the working temperature range of the galvanic pile is 200-800 ℃.
In the present invention, the heat balance insulation box and the pile insulation box may be box bodies each having an insulation layer on an inner side thereof and having good air tightness.
The invention has the following effects:
the invention can efficiently and stably prepare high-purity dry hydrogen on a large scale, and can realize self-balancing self-control hydrogen preparation with low energy consumption and high material utilization rate through hydrothermal management and safety guarantee management.
Drawings
FIG. 1 is a schematic diagram of a self-balancing self-monitored high purity dry hydrogen production system according to one embodiment of the present invention;
FIG. 2 is a schematic diagram of the construction of an electrolytic stack in the high purity dry hydrogen production system of FIG. 1;
FIG. 3 is a schematic interface diagram of the cell stack incubator in the high purity dry hydrogen production system of FIG. 1;
description of the symbols:
100. a hydrogen production system; 1. a hydrogen solenoid valve; 1', nitrogen solenoid valve (safety gas solenoid valve); 2. a hydrogen inlet pressure sensor; 2', a safety gas pressure sensor; 2 '', an air inlet pressure sensor; 3. a hydrogen mass flow controller; 3', a safety gas mass flow controller; 4. a blower; 5. a water pump; 6. a steam flow controller; 7. a wet tail gas circulating pump; 8. an air heat exchanger; 9. a hydrogen gas heat exchanger; 10. a thermally balanced heater; 11. a heat balance incubator; 12. a galvanic pile; 13. a galvanic pile incubator; 14. a hydrogen sensing alarm (sensing alarm); 15. an oxygen concentration sensor; 16. a moisture content sensor; 17. a control module; 18. an external power supply; 19. a room-temperature hydrogen input line (hydrogen circulation line); 19', a safety gas line; 20. a high-temperature hydrogen gas input line (hydrogen gas circulation line); 21. a high-temperature hydrogen gas discharge line (hydrogen gas discharge line); 22. a low-temperature hydrogen gas discharge line (hydrogen gas discharge line); 23. a hydrogen outlet pressure sensor; 23', a wet tail gas outlet pressure sensor 24 and a hydrogen circulating pump; 25. a finished product hydrogen outlet; 26. an air supply line; 27. a water supply line; 28. a water vapor supply line; 29. a wet tail gas circulation pipeline; 30. a mixed gas pipeline; 31. a high temperature wet tail gas line; 32. a low temperature wet tail gas line; 121. an electrolytic cell; 122. a dispenser; 1221. a galvanic pile hydrogen inlet; 123. a current collector; 1231. a galvanic pile hydrogen outlet; 124. a positive electrode lead; 125. a negative electrode lead; A. the direction of flow of the mixed gas; 131. a stainless steel housing; 132. a thermal insulation material; 133. a galvanic pile hydrogen inlet interface; 134. a galvanic pile hydrogen outlet interface; 135. a mixed gas inlet interface of the electric pile; 136. a wet tail gas outlet interface of the galvanic pile; 137. a positive electrode lead terminal; 138. and a negative lead terminal.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Disclosed herein is a self-balancing self-controlled high-purity dry hydrogen production system (hereinafter referred to as "hydrogen production system") capable of producing high-purity dry hydrogen with low energy consumption and high energy utilization. FIG. 1 is a schematic diagram of a hydrogen production system 100 according to one embodiment of the invention.
The hydrogen preparation system 100 can realize efficient and stable large-scale preparation of high-purity dry hydrogen, can automatically control by utilizing tail gas discharged by a galvanic pile and heat carried by the tail gas, realizes heat balance and improves the energy efficiency of the system. As shown in fig. 1, the high purity dry hydrogen production system 100 includes a stack 12, a material supply module, a scavenging module, a thermal management module, a safety and security module, a control module 17, and an external power supply 18.
[ electric pile ]
The stack 12 is a core element of the hydrogen production system 100, and mainly uses electric energy to electrolyze water vapor to produce hydrogen. Fig. 2 is a schematic view of the structure of the electrolytic stack 12. As shown in fig. 2, in the present embodiment, the stack 12 is a proton conductor type electrolytic stack, and includes a plurality of electrolytic cells 121, a distributor 122, and a current collector 123.
The electrolytic cell 121 is a proton conductor type electrolytic cell, is formed in a substantially hollow tubular shape, and includes a hydrogen electrode located on the inside, an air electrode located on the outside, and an electrolyte located between the hydrogen electrode and the air electrode. The composition of the electrolytic cell 121 is based on BaCe 1-x-y Zr x M y O 3 (BCZM for short) proton conductor material, wherein x can be 0-0 x-0.9, Y can be 0-0Y-0.2, and x + Y is 0-1, M = Y, In, Yb and other elements. In this embodiment, the electrolyte may be made of BCZY material (i.e., M is Y element), the air electrode is made of composite oxide of material such as LSC (lanthanum strontium cobaltate), LSM (lanthanum strontium manganate) or LSN (lanthanum strontium nickelate) and BCZY material, and the hydrogen electrode is made of composite oxide of Ni and BCZY material. According to the type of the proton conductor material, the working temperature range of the stack 12 can cover 200-800 ℃, and the more preferable working temperature range is 550-700 ℃.
The external power source 18 for providing power to the stack 12 may be a dc constant current power source, and the source of the power may be a power grid, or distributed renewable power such as photovoltaic, wind power, biomass, or hydroelectric power.
When hydrogen is produced by electrolyzing water in the cell stack 12, as shown in fig. 2, a mixture gas containing water vapor and air is introduced to the air electrode side of the plurality of electrolytic cells 121 in the direction of arrow a, and hydrogen is supplied to the hydrogen electrode side of the plurality of electrolytic cells 121 through the distributor 122 via the cell stack hydrogen inlet 1221, water in the mixture gas on the outer side loses electrons at the air electrode and decomposes into protons, and the protons are conducted to the hydrogen electrode on the inner side via the electrolyte to obtain electrons of an external circuit and generate hydrogen gas, and then the hydrogen gas is discharged to the cell stack hydrogen outlet 1231, so that dry pure hydrogen gas can be produced without additional treatment.
The electric pile 12 is connected with the material supply module and the scavenging module, electrolyzes water vapor in the mixed gas from the material supply module, and discharges the prepared hydrogen to a high-temperature hydrogen discharge pipeline 21 which is described later under the driving of hydrogen which is taken as scavenging gas from the scavenging module. Specifically, the mixed gas of water vapor and air enters the electrolytic stack 12 along the direction of arrow a to contact the air electrode located on the outer side, oxygen and protons are generated after water electrolysis, and the protons are transported by the electrolyte to enter the hydrogen electrode on the inner side to generate hydrogen. The hydrogen gas for purging from the scavenging module is distributed from the stack hydrogen inlet 1221 to the hydrogen electrode side (tubular internal space) of each electrolytic cell 121 via the distributor 122, the produced hydrogen gas is blown off, and the collector 123 collects the hydrogen gases and connects them to the stack 12 as a hydrogen gas discharge line, a high-temperature hydrogen gas discharge line 21 described later. Since the hydrogen electrode is not in contact with water vapor at all, high-purity dry hydrogen gas can be produced by the stack 12.
[ Material supply Module ]
The material supply module is mainly used for supplying mixed gas containing water vapor and air to the electric pile 12. As shown in fig. 1, the material supply module includes: the system comprises an air heat exchanger 8, an air supply pipeline 26, a water supply pipeline 27, a water vapor supply pipeline 28, a mixed gas pipeline 30 for supplying mixed gas from the air heat exchanger 8 to the electric pile 12, a high-temperature wet tail gas pipeline 31 for discharging wet tail gas from the electric pile 12 to the air heat exchanger 8, and a low-temperature wet tail gas pipeline 32 for discharging low-temperature wet tail gas after heat exchange from the air heat exchanger 8.
The air heat exchanger 8 is a high temperature resistant heat exchanger with a compact structure such as a plate-fin type and small pressure resistance, and heats the mixed gas containing water vapor and air by using the high temperature wet tail gas discharged from the electrolytic stack 12 as a heat source.
An air supply line 26 is connected to the air heat exchanger 8, primarily for supplying air from an external air source. The air supply line 26 is provided with a blower 4 controlled by the control module 17.
A water supply line 27 is connected to the air heat exchanger 8 and is primarily used to supply water from an external source, which may be deionized water. A water pump 5 controlled by a control module 17 is provided on the water supply line 27.
A water vapour supply line 28 is also connected to the air heat exchanger 8, primarily for supplying water vapour from an external source of steam. A steam flow controller 6 for detecting and controlling the flow rate of the steam, which is controlled by the control module 17, is provided on the steam supply line 28. In the present embodiment, water and steam are independently supplied to the air heat exchanger 8 through the water supply line 27 and the steam supply line 28, respectively, but the water supply line 27 and the steam supply line 28 may be combined into a common line through which water and steam are simultaneously supplied to the hydrogen production system 100.
The air supplied from the air supply line 26, the deionized water supplied from the water supply line 27, and the steam supplied from the steam supply line 28 are premixed in the air heat exchanger 8, and heat-exchanged with the high-temperature wet tail gas from the high-temperature wet tail gas line 31 described later, so that the deionized water is completely evaporated into steam, and the steam is supplied to the mixed gas line 30 as a mixed gas in which the steam and the air are mixed. A thermal balance heater 10 controlled by the control module 17 is arranged on the mixture line 30, and the thermal balance heater 10 is used for raising the temperature of the mixture again. The control module 17 determines whether to activate the thermal balance heater 10 for heating according to the load state of the stack 12 and the temperature state of each component in the hydrogen production system 100, which will be described later.
The heated mixed gas enters the electric pile 12 through the mixed gas pipeline 30 along the arrow a direction in fig. 2, and is electrolyzed in the electric pile 12 to form wet tail gas with low moisture content (i.e. water vapor content), and the wet tail gas is discharged to the high-temperature wet tail gas pipeline 31. The high-temperature wet tail gas enters the air heat exchanger 8 to exchange heat as described above, and condensed water and low-temperature wet tail gas are generated after heat exchange and are discharged to the low-temperature wet tail gas pipeline 32. In the present embodiment, as shown in fig. 1, a condensed water storage region for storing condensed water generated after heat exchange is formed in the lower portion of the air heat exchanger 8. The water pump 5 is connected to the condensed water storage area through a condensed water pipeline, a liquid level sensor, not shown, is arranged on the air heat exchanger 8, the liquid level sensor monitors the liquid level of the condensed water and is linked with the water pump 5 under the control of the control module 17 to supply the condensed water to the air heat exchanger 8 through the water supply pipeline 27 in a circulating mode again, and therefore energy consumption of the system can be reduced.
In the present embodiment, the low-temperature wet tail gas pipeline 32 is provided with the wet tail gas circulation pump 7 on the downstream side of the air heat exchanger 8, and the wet tail gas circulation pipeline 29 branches off from the wet tail gas circulation pump 7. The wet tail gas circulation line 29 is mainly used for returning a part of the wet tail gas flowing in the low-temperature wet tail gas line 32 to the air heat exchanger 8, and as shown in fig. 1, the wet tail gas at the split position is mixed with the air supplied by the air supply line 26, the deionized water supplied by the water supply line 27 and the water vapor supplied by the water vapor supply line 28 in the air heat exchanger 8 to raise the temperature, so that the steam utilization rate can be improved, and the system energy consumption can be reduced.
An oxygen concentration sensor 15 and a moisture content sensor 16 for analyzing gas components are provided in the wet tail gas circulation line 29, and a wet tail gas outlet pressure sensor 23' is provided in the low-temperature wet tail gas line 32 between the wet tail gas circulation pump 7 and the air exchanger 8, and an air inlet pressure sensor 2 ″ is also provided in the air supply line 26. Thus, the control module 17 can control the amount of air discharged from the blower 4 based on the gas flow rate in the wet exhaust gas circulation line 29 and the detection value of the oxygen concentration sensor.
[ scavenging Module ]
The scavenging module is mainly used for returning a part of hydrogen discharged by the electric pile 12 to the electric pile 12 so as to enter the electric pile 12 for purging and carry out the produced hydrogen. The scavenging module comprises: a hydrogen gas discharge line that discharges hydrogen gas from the stack 12; a hydrogen circulation line for distributing hydrogen to the stack 12; and a hydrogen heat exchanger 9 for heat-exchanging the hydrogen gas in the hydrogen circulation line and the hydrogen gas in the hydrogen discharge line.
Specifically, the hydrogen heat exchanger 9 is a high-temperature resistant heat exchanger with a compact structure such as a plate-fin type and small pressure resistance, and heats a small amount of room-temperature scavenging hydrogen entering the electrolytic stack 12 by using high-temperature hydrogen discharged from the electrolytic stack 12 as a heat source.
The hydrogen gas discharge line includes a high-temperature hydrogen gas discharge line 21 that outputs hydrogen gas from the stack 12 to the hydrogen heat exchanger 9 and a low-temperature hydrogen gas discharge line 22 that discharges hydrogen gas from the hydrogen heat exchanger 9. The hydrogen circulation line includes a room-temperature hydrogen input line 19 that branches hydrogen from a low-temperature hydrogen discharge line 22 and supplies the hydrogen to the hydrogen heat exchanger 9, and a high-temperature hydrogen input line 20 that supplies hydrogen for scavenging from the hydrogen heat exchanger 9 to the stack 12.
The low-temperature hydrogen discharge line 22 discharges the product hydrogen to the outside through a product hydrogen discharge port 25, and a hydrogen circulation pump 24 controlled by the control module 17 is provided on the low-temperature hydrogen discharge line 22 on the downstream side of the hydrogen heat exchanger 9. In addition, a hydrogen outlet pressure sensor 23 for monitoring the hydrogen pressure on the low-temperature hydrogen discharge line 22 is also arranged on the low-temperature hydrogen discharge line 22 between the hydrogen circulation pump 24 and the hydrogen heat exchanger 9.
The input end of the room temperature hydrogen input pipeline 19 is communicated with other hydrogen sources such as steel cylinders on one hand, hydrogen purging is carried out at the initial stage of system temperature rise, on the other hand, the room temperature hydrogen input pipeline is connected with the low temperature hydrogen discharge pipeline 22 through the hydrogen circulating pump 24, and the output end is connected with the hydrogen heat exchanger 9 as described above. A hydrogen solenoid valve 1 for opening and closing the room-temperature hydrogen input pipeline 19 under the control of the control module 17, a hydrogen inlet pressure sensor 2 for detecting the pressure of hydrogen flowing on the room-temperature hydrogen input pipeline 19, and a hydrogen mass flow controller 3 for detecting the mass flow of hydrogen flowing on the room-temperature hydrogen input pipeline 19 are arranged on the room-temperature hydrogen input pipeline 19. The control module 17 controls the hydrogen circulation pump 24 and the hydrogen solenoid valve 1 based on the detection values of the hydrogen inlet pressure sensor 2 and the hydrogen mass flow controller 3, and adjusts the amount of hydrogen branched from the low-temperature hydrogen discharge pipeline 22.
As described above, the hydrogen gas branched from the low-temperature hydrogen gas discharge line 22 is introduced into the hydrogen heat exchanger 9 through the room-temperature hydrogen gas input line 19, exchanges heat with the high-temperature hydrogen gas from the cell stack 12 flowing through the high-temperature hydrogen gas discharge line 21, and is introduced into the cell stack 12 again through the high-temperature hydrogen gas input line 20 after the temperature is raised. This allows the hydrogen gas generated by scavenging the inside of the cell stack 12 to be utilized, and also allows the scavenging hydrogen gas to be heated by the heat of the high-temperature hydrogen gas discharged from the cell stack 12, thereby saving energy consumption.
[ safety guarantee Module ]
In order to ensure the safety of the system, a safety module connected to the scavenging module is further provided in the hydrogen production system 100. The safety and security module stops the operation of the stack 12 and supplies safety gas to the stack 12 when a leakage is detected. The safety guarantee module comprises a safety gas pipeline 19', a hydrogen sensing alarm 14 and a three-way regulating valve.
Specifically, the room-temperature hydrogen gas input line 19 is provided with a three-way regulating valve downstream of the hydrogen mass flow controller 3. One end of the safety gas pipeline 19' is connected with an external safety gas supply source such as a steel cylinder, and the other end is connected with the room temperature hydrogen input pipeline 19 through a three-way regulating valve. A safety gas solenoid valve 1 ' for opening and closing the safety gas line 19 ' under the control of the control module 17, a safety gas pressure sensor 2 ' for detecting the pressure of safety gas flowing through the safety gas line 19 ', and a safety gas mass flow controller 3 ' for detecting the mass flow of safety gas flowing through the safety gas line 19 ' are provided in the safety gas line 19 '. Thereby, the supply of hydrogen or the safety gas to the stack 12 can be switched by controlling the three-way regulating valve.
With the above structure, the safety assurance module judges whether hydrogen leakage occurs according to the detection values of the hydrogen inlet pressure sensor 2 provided on the room-temperature hydrogen input pipeline 19 and the hydrogen outlet pressure sensor 23 provided on the low-temperature hydrogen discharge pipeline 22. When the hydrogen leakage is judged to occur, the hydrogen sensing alarm 14 gives an alarm and cuts off the external power supply 18, and the three-way regulating valve is controlled to block the room-temperature hydrogen input pipeline 19 and open the safe gas pipeline 19'. Specifically, the safety gas solenoid valve 1 'and the safety gas mass flow controller 3' for purging the safety gas are activated, whereby hydrogen leakage which may occur to the parts and the stack can be detected and responded in time, ensuring man-machine safety to prevent an accident.
In the present embodiment, the safety gas is nitrogen, but the safety gas is not limited thereto, and may be an inert gas such as Ar or He.
[ thermal management Module ]
In the invention, in order to efficiently and stably produce hydrogen with low energy consumption, a thermal management module for performing thermal management on the galvanic pile 12, the material supply module and the scavenging module is further designed. The thermal management module comprises: the thermal balance heater 10 disposed on the mixed gas line 30; a heat balance incubator 11; and a stack incubator 13.
As shown in fig. 1, the heat balance and insulation box 11 is mainly used for accommodating and insulating the air heat exchanger 8, the hydrogen heat exchanger 9, and the heat balance heater 10. More specifically, the heat Balance and insulation box 11 is a box body having an insulating layer on the inner side thereof and having good air tightness, and an air heat exchanger 8, a hydrogen heat exchanger 9, a heat Balance heater 10, and a connection pipe around the heat exchanger and the heat Balance heater are wrapped therein, and an air inlet port and an air outlet port are provided on the outer wall thereof so as to be in contact with a response port of the stack insulation box 13, thereby constituting a BOP (Balance of Plant, i.e., a thermal Balance member including a heat exchanger, a heater, and the like) hot zone.
The stack incubator 13 is mainly used to wrap and insulate the stack 12, thereby forming a stack hot zone. More specifically, the stack thermal insulation box 13 is a box body with an insulating layer on the inner wall and good air tightness, and fig. 3 is a schematic interface diagram of the stack thermal insulation box 13. As shown in fig. 3, the stack incubator 13 includes a stainless steel casing 131 on the outside and an insulating material 132 on the inside. The stainless steel housing 131 is used for connection to the stack 12 on one side and to the BOP hot section on the other. Specifically, a stack hydrogen inlet interface 133 for connecting the high-temperature hydrogen input pipeline 20, a stack hydrogen outlet interface 134 for connecting the high-temperature hydrogen discharge pipeline 21, a stack mixed gas inlet interface 135 for connecting the mixed gas pipeline 30, a stack wet tail gas outlet interface 136 for connecting the high-temperature wet tail gas pipeline 31, and a positive electrode 137 and a negative electrode lead terminal 138 for leading out the positive electrode lead 124 and the negative electrode lead 125 are formed on the stainless steel casing 131, and the two terminals are well insulated from each other.
In addition, the thermal management module includes temperature sensors (typically type K thermocouples) disposed on the various pipes and components within the system.
As described above, in the present invention, the control module 17 thermally manages the hydrogen production system 100 through the thermal management module. Specifically, the control module 17 reads data from each temperature sensor, monitors the operating temperature of the stack 12, and activates the thermal balance heater 10 to heat the mixture when necessary. The hydrogen production system 100 is thus thermally balanced by the thermal management module in a manner that ensures that the stack 12 operates within a specified temperature range, depending on the load condition of the stack 12. More specifically, the control module 17 controls the thermal balance heater 10 to heat the mixture in a manner that the electric stack 12 is ensured to operate within a specified temperature range (for example, 500 to 750 ℃) according to the power output by the external power source 18 to the electric stack 12. When the low working temperature of the electric pile 12 is detected, the control module 17 controls the heat balance heater 10 to heat the mixed gas, so as to increase the temperature of the electric pile 12. When the operating temperature of the stack 12 is high, the control module 17 turns off the thermal balance heater 10 and appropriately reduces the load current of the stack 12, thereby reducing the stack temperature, and thus repeating the above process to achieve dynamic balance of the operating temperature of the stack 12.
In addition, the control module 17 calculates the gas composition in the wet tail gas through the oxygen concentration sensor 15 and the moisture content sensor 16, and accurately calculates the amount of deionized water and water vapor required in the mixed gas supplied to the electric pile 12 and the gas temperature after heat exchange in the air heat exchanger 8, thereby controlling the water pump 5, the water vapor flow controller 6 and the wet tail gas circulating pump 7, improving the utilization rate of the vapor and the water as much as possible, and reducing the energy consumption of the system. The self-balancing control is realized by the real-time detection values of the moisture content at the inlet side of the galvanic pile 12, the electrolysis current (corresponding to the water vapor usage amount) of the galvanic pile 12, the power of the wet tail gas circulating pump 7 and the hydrogen circulating pump 24, the flow rate of the water pump 5 and the water vapor flow control, and the feedback control after the calculation of the control module 17.
Specifically, the control module 17 controls the power of the wet tail gas circulation pump 7 based on the detection value of the moisture content sensor, that is, the moisture content in the low-temperature wet tail gas pipeline 32, returns a part of the wet tail gas to the air heat exchanger 8, and controls the power of the blower 4 based on a comparison between the detection value of the oxygen concentration sensor 15 in the wet tail gas circulation pipeline 29 and the oxygen content value in the air, and decreases the power of the blower 4 when the detection value of the oxygen concentration sensor 15 is high, and increases the power of the blower 4 when the detection value of the oxygen concentration sensor 15 is low. In addition, the control module 17 returns at least a part of the condensed water generated after heat exchange to the water pump 5 according to the detection value of the liquid level sensor, and the water pump 5 is sent to the air heat exchanger 8 through the water supply pipeline for recycling. Meanwhile, the control module calculates the difference between the moisture content required by the galvanic pile 12 and the moisture content in the wet tail gas circulation pipeline 29 and the moisture content in the water vapor supply pipeline 28, and adjusts the water flow supplied by the water pump 5 according to the difference. The control module also calculates the difference between the required moisture content of the stack 12 and the moisture content in the wet tail gas recirculation line 29 and the moisture content resulting from the evaporation of water supplied by the water pump 5 in the air heat exchanger 8, and adjusts the moisture content (i.e., the amount of water vapor supplied) in the water vapor supply line 28 by controlling the water vapor flow controller 6 based on the difference.
The hydrogen production system can realize efficient and stable large-scale preparation of high-purity dry hydrogen, and the designed hydrothermal management system can automatically control the temperature of the galvanic pile and the utilization of water vapor, so that the heat balance is realized, and the energy efficiency of the system is improved; the safety guarantee system can monitor hydrogen leakage possibly occurring on parts and a galvanic pile and respond immediately, and fully ensures man-machine safety.
The hydrogen production system 100 of the present invention operates by the following procedure.
Firstly, the integrated galvanic pile 12 is arranged in a galvanic pile insulation box 13, necessary gas pipeline connection and electrode lead connection are carried out, and then the galvanic pile insulation box 13 is sealed and arranged in a hydrogen production system rack of the hydrogen production system 100. And then the hydrogen heat exchanger 9, the air heat exchanger 8 and the heat balance heater 10 are connected by pipelines and then are arranged in the heat balance insulation box 11. The gas inlets and outlets of the two heat preservation hot boxes are connected in a butt joint mode, specifically, after the high-temperature hydrogen input pipeline 20, the high-temperature hydrogen discharge pipeline 21, the mixed gas pipeline 30, the high-temperature wet tail gas pipeline 31 and the low-temperature wet tail gas pipeline 32 are connected, the two heat preservation hot boxes are connected with other pipelines in the system. Two electrode leads of the cell stack 12 are connected to an external power supply 18, a control module 17, and the like via electrode terminals on the cell stack incubator 13.
Then the air blower 4 is controlled to convey air into the air heat exchanger 8 at a certain air speed for heating, meanwhile, the water pump 4 is controlled to convey deionized water into the air heat exchanger 8 at a certain flow rate for complete evaporation, the air and the water vapor are mixed and then enter the heat balance heater 10, the mixture enters the galvanic pile heat preservation box 13 for heating the galvanic pile 12 after being heated again, and then the mixture flows out of the galvanic pile 12 and enters the air heat exchanger 8. The hydrogen circulating pump 24 is controlled to convey hydrogen into the hydrogen heat exchanger 9 at a certain flow rate, the hydrogen enters the distributor 122 of the galvanic pile 12 after being heated, the hydrogen enters the hydrogen heat exchanger 9 after heating the galvanic pile 12, the cooled hydrogen enters the hydrogen circulating pump, a part of the hydrogen enters the galvanic pile 12 again after being circulated, and the other part of the hydrogen enters a hydrogen storage tank and other use ends through the finished product hydrogen outlet 25. Thereby raising the stack 12 to the operating temperature at a rate by the hot fluid.
When the electric pile 12 is heated to the working temperature (for example, 500 to 750 ℃) and is basically stable, the external power supply 18 is controlled to be input into the electric pile 12, the hydrogen preparation system 100 starts to produce hydrogen, the control module 17 monitors and keeps the stable work of the electric pile 12, and meanwhile, the hydro-thermal management and the safety guarantee management of the hydrogen preparation system 100 are carried out.
Compared with the existing hydrogen production system, the invention has the following advantages.
1) High hydrogen purity, no need of separation and purification: because the water vapor is arranged on one side of the air electrode, and the electric pile 12 as a core element is a proton conductor type electric pile 12, the hydrogen prepared by the system is dry high-purity hydrogen, separation and purification are not needed, the flow steps of the system are reduced, and the system cost is reduced.
2) High energy efficiency and low energy consumption for hydrogen production: because the activation energy and the internal resistance of the high-temperature electrolytic cell in the electric pile 12 are lower, the hydrogen production efficiency of the system is high, and the power consumption of every cubic meter of hydrogen is 3.5-4 kilowatt-hours.
3) High reliability: the BOP hot area and the galvanic pile hot area are integrated in a modularization mode, partition management is facilitated, maintenance is convenient, and the overall reliability of the system is high.
4) No complex parts, easy realization of system compactness and strong power configuration flexibility.
The following examples are provided to further illustrate the invention.
Examples
According to the structure and the flow, the hydrogen preparation system is integrated, stainless steel pipelines are selected for each pipeline, and the electromagnetic valves, the pressure sensors, the mass flow controllers and the heat exchangers are connected according to the gas flow direction to form the modules and the BOP hot area. As shown in fig. 2, a stack 12 composed of 64 Ba-based tube-shaped proton conductor-type electrolytic cells was integrated. The integrated stack 12 is loaded into the stack incubator 13, as shown in fig. 3, gas piping connection and electrode lead connection are performed through the respective ports on the stainless steel case 131, then the stack incubator 13 is sealed and loaded into the hydrogen gas production system, the gas inlet/outlet of the stack incubator 13 is connected to the respective gas inlet/outlet of the thermal equilibrium incubator 11, and the electrode terminal of the stack incubator 13 is connected to the external power supply 18.
The air blower 4 is controlled to convey air into the air heat exchanger 8 at a certain air speed for heating, the water pump 5 is controlled to convey deionized water to the air heat exchanger 8 at a certain flow speed for complete evaporation, mixed gas obtained by mixing air and steam enters the heat balance heater 10, the mixed gas enters the galvanic pile heat insulation box 13 after being heated again, and the mixed gas flows out of the galvanic pile heat insulation box 13 after heating the galvanic pile 12 and enters the air heat exchanger 8. The control module 17 controls the hydrogen circulating pump 24 to convey hydrogen into the hydrogen heat exchanger 9 at a certain flow rate, the hydrogen enters the distributor 122 in the galvanic pile 12 after being heated, the hydrogen flows out of the galvanic pile heat preservation box 13 after heating the galvanic pile 12 and enters the hydrogen heat exchanger 9, the cooled hydrogen tail gas enters the hydrogen circulating pump 24, one part of the hydrogen tail gas circulates into the galvanic pile 12 again, and the other part of the hydrogen tail gas enters the hydrogen storage tank and other use ends. Thereby heating the stack 12 at a rate by the hot fluid.
After the temperature of the galvanic pile 12 is raised to 500-750 ℃ and basically stable, the external power supply 18 is controlled to supply power to the galvanic pile 12, the hydrogen preparation system starts to produce hydrogen, the control module 17 monitors and keeps the stable work of the galvanic pile 12, and the automatic control of heat balance and material circulation is carried out.
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (13)
1. A self-balancing self-control high-purity dry hydrogen preparation system which is characterized in that,
the method comprises the following steps:
the galvanic pile is used for preparing hydrogen by electrolyzing water vapor by using electric energy;
a material supply module supplying a mixed gas containing water vapor and air to the electric pile;
a scavenging module which returns part of the hydrogen discharged by the electric pile to the electric pile;
a thermal management module for thermally managing the material supply module, the scavenging module and the galvanic pile;
a safety and security module stopping the operation of the stack and supplying safety gas to the stack when leakage is detected;
an external power supply for supplying power; and
a control module;
the control module controls the material supply module, the scavenging module and the thermal management module to circularly utilize a plurality of gases exhausted by the electric pile and heat carried by the gases in a mode of maintaining the electric pile to work in a specified working temperature interval.
2. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 1,
the electric pile comprises a plurality of electrolytic cells, a distributor for distributing hydrogen to the plurality of electrolytic cells and a current collector for collecting hydrogen from the plurality of electrolytic cells;
the plurality of electrolytic cells are proton conductor type electrolytic cells formed in a tubular shape, including an air electrode on the outside, a hydrogen electrode on the inside, and an electrolyte composed of a proton conductor material between the air electrode and the hydrogen electrode;
the stack also includes a pair of high temperature resistant wires for introducing electrical current.
3. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 1 or 2,
the scavenging module includes:
a hydrogen gas discharge line that discharges hydrogen gas from the stack;
a hydrogen circulation line for supplying hydrogen to the stack; and
a hydrogen gas heat exchanger that exchanges heat between the hydrogen gas in the hydrogen circulation line and the hydrogen gas in the hydrogen discharge line;
a hydrogen outlet pressure sensor is arranged on the hydrogen discharge pipeline at the downstream side of the hydrogen heat exchanger;
the hydrogen circulation pipeline is connected with the hydrogen discharge pipeline through a hydrogen circulation pump, and part of hydrogen in the hydrogen circulation pipeline is distributed to the hydrogen discharge pipeline.
4. The self-balancing self-controlled high purity dry hydrogen production system according to any one of claims 1 to 3,
the hydrogen circulation pipeline is provided with a hydrogen electromagnetic valve, a hydrogen inlet pressure sensor and a hydrogen mass flow controller at the upstream side of the hydrogen heat exchanger;
the control module controls the hydrogen circulating pump and the hydrogen solenoid valve based on detection values of the hydrogen inlet pressure sensor and the hydrogen mass flow controller, and adjusts a hydrogen flow rate branched from the hydrogen circulating pipeline to the hydrogen exhaust pipeline.
5. The self-balancing self-controlled high purity dry hydrogen production system according to any one of claims 1 to 4,
the security assurance module includes:
a hydrogen sensing alarm;
a safety gas pipeline provided with a safety gas electromagnetic valve, a safety gas pressure sensor and a safety gas mass flow controller; and connecting the safety gas pipeline with the hydrogen circulating pipeline through a three-way regulating valve;
the safety guarantee module judges whether hydrogen leakage occurs according to detection values of the hydrogen inlet pressure sensor and the hydrogen outlet pressure sensor, and cuts off the external power supply when the leakage is judged to occur, controls the three-way regulating valve to block the hydrogen circulation pipeline and open the safety gas pipeline;
the safety gas is nitrogen or inert gas.
6. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 1,
the material supply module comprises:
an air heat exchanger;
an air supply pipeline for supplying air to the air heat exchanger;
a water pump is arranged, and a water supply pipeline is used for supplying water to the air heat exchanger;
a steam supply line supplying steam to the air heat exchanger;
a mixed gas line for sending the mixed gas from the air heat exchanger to the electric pile;
a high-temperature wet tail gas pipeline connected with the air heat exchanger and used for discharging wet tail gas from the electric pile; and
a low-temperature wet tail gas pipeline for discharging the low-temperature wet tail gas subjected to heat exchange from the air heat exchanger;
a wet tail gas circulating pump is arranged on the lower side of the low-temperature wet tail gas pipeline, which is closer to the air heat exchanger than the low-temperature wet tail gas pipeline, and the wet tail gas circulating pump is branched out of the wet tail gas circulating pipeline;
and the air, the water and the water vapor are subjected to heat exchange with wet tail gas in the wet tail gas circulating pipeline in the air heat exchanger and then heated and mixed to form the mixed gas.
7. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 6,
an oxygen concentration sensor and a moisture content sensor for analyzing gas components are arranged on the wet tail gas circulating pipeline;
a wet tail gas outlet pressure sensor is arranged on the wet tail gas pipeline between the wet tail gas circulating pump and the air exchanger;
an air inlet pressure sensor is also arranged on the air supply pipeline;
the control module controls as follows:
controlling the power of the wet tail gas circulating pump according to the detection value of the moisture content sensor, and returning a part of wet tail gas to the air heat exchanger;
and controlling the power of the blower according to the comparison between the detection value of the oxygen concentration sensor in the wet tail gas circulating pipeline and the oxygen content value in the air, reducing the power of the blower when the detection value of the oxygen concentration sensor is high, and increasing the power of the blower when the detection value of the oxygen concentration sensor is low.
8. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 6 or 7,
the air heat exchanger is also provided with a condensed water storage area for storing condensed water generated by heat exchange at the lower part, and the condensed water storage area is connected with the water pump through a condensed water pipeline;
a liquid level sensor for monitoring the liquid level of the condensed water is arranged on the condensed water storage area;
and the control module returns at least one part of the condensed water to the water pump for recycling according to the detection value of the liquid level sensor.
9. The self-balancing self-controlled high purity dry hydrogen production system according to any one of claims 6 to 8,
the control module adjusts the water flow supplied by the water pump according to the difference value between the moisture content required by the galvanic pile and the moisture content in the wet tail gas circulating pipeline and the moisture content in the water vapor supply pipeline;
the water is deionized water.
10. The self-balancing self-controlled high purity dry hydrogen production system according to any one of claims 6 to 9,
the steam supply pipeline is also provided with a steam flow controller for detecting and controlling the flow of the steam;
the control module adjusts the moisture content in the water vapor supply pipeline by controlling the water vapor flow controller according to the moisture content required by the galvanic pile, the moisture content in the wet tail gas circulation pipeline and the moisture content obtained by evaporating water supplied by the water pump in the air heat exchanger.
11. The self-balancing self-controlled high purity dry hydrogen production system according to any one of claims 1 to 10,
the thermal management system comprises:
a thermal balance heater disposed on the mixed gas line;
the heat balance insulation box is used for insulating the hydrogen heat exchanger, the air heat exchanger and the heat balance heater;
a galvanic pile heat insulation box for insulating the galvanic pile; and
a temperature sensor;
the control module controls the heat balance heater to heat the mixed gas in a mode of ensuring that the electric pile works in a specified temperature interval according to the power output by the external power supply to the electric pile.
12. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 11,
the working temperature range of the galvanic pile is 200-800 ℃.
13. The self-balancing self-controlled high-purity dry hydrogen production system according to claim 6,
the heat balance insulation box and the galvanic pile insulation box are box bodies with heat insulation layers arranged on the inner sides and good air tightness.
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